Divalent Multilinking Bonds Control Growth and Morphology of Nanopolymers.

Yan Xiong,Deniz Mostarac,Sofia Kantorovich,Guolong Zhu,Yonggang Ke,Brian Minevich,Oleg Gang,Zhiwei Lin,Pedro A Sánchez,Qiuyuan Peng

doi:10.1021/acs.nanolett.1c03009

Yan Xiong, Deniz Mostarac + Show 8 more

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https://doi.org/10.1021/acs.nanolett.1c03009

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Assembly of nanoscale objects into linear architectures resembling molecular polymers is a basic organization resulting from divalent interactions. Such linear architectures occur for particles with two binding patches on opposite sides, known as Janus particles. However, unlike molecular systems where valence bonds can be envisioned as pointlike interactions nanoscale patches are often realized through multiple molecular linkages. The relationship between the characteristics of these linkages, the resulting interpatch connectivity, and assembly morphology is not well-explored. Here, we investigate assembly behavior of model divalent nanomonomers, DNA nanocuboid with tailorable multilinking bonds. Our study reveals that the characteristics of individual molecular linkages and their collective properties have a profound effect on nanomonomer reactivity and resulting morphologies. Beyond linear nanopolymers, a common signature of divalent nanomonomers, we observe an effective valence increase as linkages lengthened, leading to the nanopolymer bundling. The experimental findings are rationalized by molecular dynamics simulations.

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Of nanoscale objects into linear architectures resembling molecular polymers is a basic organization resulting from divalent interactions
Of nano-objects into linear architectures offers an attractive route for forming “nanopolymers”,1−9 analogous to molecular polymers. These linear architectures are composed of inorganic nanoparticles[1,10,11] or colloids,[12−14] allowing for manipulation of plasmonic,[15−20] magnetic,[21−24] electronic[25−27] and mechanical[28,29] properties
One of the key parameters dictating a morphology assembled from Janus particles is the relative size of each patch.[14,36,37]

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Of nanoscale objects into linear architectures resembling molecular polymers is a basic organization resulting from divalent interactions. This regime has been only mapped out for polymerizing divalent patchy particles via short linkages.[52,53] In our study, the divalent nanomonomers are DNA-based cuboids, so-called DNA nanochamber (DNC),[52] on which length-adjustable and number-prescribed single-stranded DNA (ssDNA), capable of forming molecular linkages, are zoned as two patches (Figure 1).

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